Method for manufacturing an elastic ceramic matrix composite

ABSTRACT

Disclosed are: damage-resistant ECMCs that need to work and remain elastic between minus 120° C. and positive 300° C.; ECMCs that need to be able to contain a flame of 1900° C. for more than 90 minutes; and composite structures, especially highly stressed structures. One of the characteristic problems of ceramic matrices is their fragility. Indeed, when a fracture starts, it propagates easily in the matrix. Disclosed are elastic ceramic matrix composites (ECMCs), for which: the ceramic matrix is split into solid “ceramic microdomains” (CMDs); the CMDs are connected to one another by a dense network of “elastic microelements” (EMEs); and the bonds between the EMEs and the CMDs are strong chemical bonds, preferably covalent.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of application Ser. No. 16/334,268, filed on Mar. 18, 2019, which is the National Phase under 35 U.S.C. § 371 of International Application No. PCT/FR2016/000140, filed on Sep. 16, 2016, all of which are hereby expressly incorporated by reference into the present application.

FIELD OF THE INVENTION

The present invention relates to a method for Ceramic Composites, Elastic Matrix, (CCEM) production. This damage tolerant having mechanical properties similar to those of epoxy-based composites. We already know processes for making ceramics, but they are dramatically fragile!

In the state of the prior art, the procedure to produce ceramic is as follows:

Step 1: Silica is dissolved in an alcaly solution (preferably Ph11) consisting of water (5) (FIG. 5 ) and an alcaly, for example KOH (or NaOH) (6) (FIG. 5 ) a transparent liquid is then obtained containing silicon atoms positioned in the center of tetrahedral whose vertices are formed by four oxygen atoms, each oxygen atom bearing a hydrogen (system called silicate (4) (FIG. 5 )) floating in the said liquid. We thus have a so called “mineral hardener”

Step 2: then pouring said mineral hardener on dry powder (3) (FIG. 5 ) for example Metakaolin (mineral matrix class b), then intimately mixed, a “slip” is obtained.

Step 3: It is then possible, for example, with the slip, to impregnate a fibrous reinforcement, in order to obtain a “ceramic composite”, it is then necessary to place the assembly in a hermetic mold and then to heat, for example to 60° C. for 40 minutes (or 6 minutes at 120° C.) to obtain a polycrystallization (2) (FIG. 5 ) of oxide ceramic, see FIG. 3 . (CMD). This type of ceramic composite has particularly poor mechanical properties. The flaws of this process are that it leads to the manufacture of an extremely fragile ceramic that breaks at the slightest stress, especially in tension and shear.

TECHNICAL PROBLEM TO BE RESOLVED

Composite matrices consisting of layers containing reinforcing fibers (unidirectional woven, felt, or mat) and matrix: organic, mineral, or ceramic, are increasingly used to make light structures such as those described in the art. ‘invention’. When placed under significant stress or during shocks, these composite structures are subject to deformation. The conventional ceramic matrices are extremely fragile and do not tolerate significant deformations.

The goal of CCEM is to behave mechanically and to perform as organic matrices, while having a much wider thermal range of use, and a significantly lower cost of ownership. The subject of the present invention is a method developed for producing a ceramic composite with an elastic matrix, which is characterized by the fact that it comprises the following steps:

Step 1: an admixture comprising at least one of the following elements is dispersed in water: an alkali (or) an acid, to obtain “an adjuvant in aqueous solution”,

Step 2: then, in the said adjuvant in aqueous solution, an additive is reacted to obtain a “mineral hardener”

Step 3: the preparation of a “fluid silicone homopolymer with active terminations” is carried out,

Step 4: Finally we prepare a “mineral resin powder”

Step 5: said mineral hardener is poured and intimately mixed in said mineral resin powder to form a “ceramic mixture”

Step 6: the active-terminated fluid silicone homopolymer is then dispersed in the ceramic mixture to obtain said “elastic ceramic mixture”

According to another characteristic, the method is distinguished by the fact that it further comprises: a step 7, consisting in impregnating said “elastic ceramic mixture” obtained at the end of step 6, with means of “fibrous reinforcements”, we then obtain a “ceramic composite with elastic matrix”, CCME

The method includes an additional step 8, consisting in dispersing, in the mixture, a micro-reinforcement network constituted by “dendritic nanofractals”, said step 8 being carried out at one of the following occurrences: between step 5 and the step 6, between step 6 and step 7.

According to another characteristic the process is distinguished by the fact that: said alkali is constituted by a combination and at least one of the following bases: KOH=potassium hydroxide, NaOH=sodium hydroxide, CsOH=cesium hydroxide, LiOH=lithium hydroxide and the said acid being constituted by minus one of the following acids: HCl=hydrochloric acid, H2SO4=sulfuric acid, HF=hydrofluoric acid, H3PO4=phosphoric acid, to obtain an “adjuvant in aqueous solution”

-   -   said additive is constituted by at least one of the following         elements: an oxide (silicon, aluminum, magnesium, zirconium,         calcium), a metal (aluminum, magnesium, zirconium, of calcium) a         metalloid (of silicon), to obtain a “mineral hardener”     -   said mineral resin powder consists of at least one of the         following elements: *a mineral polymer [consisting of a         poly(sialate), (Si/Al ratio=1)], a mineral polymer [consisting         of a poly(sialate-siloxo), (ratio Si/Al=2)], a mineral polymer         [consisting of an aluminosilicate, poly(sialate-disiloxo),         (Si/Al ratio=3) namely (—Si—O—Al—O—)_(n) such as metakaolin         (Si₂O₅,Al₂O₂)_(n); a mineral polymer [consisting of an         aluminosilicate, poly(sialate-disiloxo), namely         (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅, Al₂O₂)_(n)         supplemented with aluminum phosphate (AlPO₄) a complex mineral         polymer [consisting of a poly(sialate-disiloxo) aluminosilicate,         (Si/Al ratio=3) namely (—Si—O—Al—O—)_(n) such as metakaolin         (Si₂O₅,Al₂O₂)_(n) and a micronized alumina namely. (Al₂O₃)]; A         complex mineral polymer [consisting of a poly(sialate-disiloxo)         aluminosilicate, (Si/Al ratio=3) namely (—Si—O—Al—O—)_(n) such         as metakaolin (Si₂O₅,Al₂O₂)_(n) and d a micronized zirconium         oxide, namely. (ZrO₂)]; a complex mineral polymer [consisting of         a poly(sialate-disiloxo) aluminosilicate, (Si/Al ratio=3) namely         (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅,Al₂O₂)_(n) of a         micronized magnesium oxide namely (MgO)]; A complex mineral         polymer [consisting of a poly(sialate-disiloxo) aluminosilicate,         (Si/Al ratio=3) namely (—Si—O—Al—O—)_(n) such metakaolin         (Si₂O₅,Al₂O₂)_(n) of a micronized calcium oxide ie (CaO)].     -   said active-terminated liquid silicone homopolymer of step 6         consists of at least one of the following terminations:         OH-terminus, H-terminus, H-terminal hybrid on one side and OH on         the other, termination alcohol (methanol), alcohol (ethanol)         terminus, to obtain said “flexible ceramic mixture”.

According to another characteristic, The process is distinguished by the fact that: “dendritic nanofractals” have nanopatatoid forms (16) of 10 to 50 nanometers in diameter aggregated together by covalent bonds to thereby form dendrites (13, 15), circumscribed in a patatoid volume of 50 to 1000 nanometers in diameter, the surface values of said dendritic nanofractals being included in a range of values whose lower limit is about 10 square meters per gram and whose upper limit, is about 750 square meters per gram (measured according to the BET method).

The process is distinguished by the fact that the dendritic nanofractals consist of a combination of at least one of the following products: *Metal oxides, for example titanium oxide TiO₂ or zirconium oxide ZrO₂, non-functionalized. *Metallic oxides, for example alumina Al₂O₃, preferentially functionalized. *Metalloid oxide such as silicon oxide, for example silicon dioxide SiO₂, boron oxide, boric anhydride by B₂O₃ anhydrous borax, preferentially functionalized. *Metalloidal oxide such as SiC silicon carbide nonfunctionalised. *Non-metals, such as phosphorus oxide, phosphoric anhydride (P₂O₅); carbon black which is colloidal carbon (graphite) nonfunctionalised.

According to another characteristic, the method is distinguished by the fact that the “fibrous reinforcements” are chosen from at least one of the following materials: *Functionalized boron fibers. *Functionalized silica. *Functionalized quartz. *Basalt functionalized preferentially. *Functionalized glass. *Unfunctionalized carbon. *Non-functionalized silicon carbide. *Functionalized ceramics (eg. alumina, alumina mullite). *Non-functionalized zirconium. *Functionalized stainless steel. *Inconel non-functionalized. *Functionalized polyisilazane. *Aramid non-functionalized *Polyethylene HD (Example DYNEEMA).

According to another advantageous characteristic:

Step 1: to disperse, an active-terminated liquid silicone homopolymer (1), for example, polydimethylsiloxanes (PDMS), very homogeneously, in the mineral powder (3) (a-class mineral matrix). This operation produces a pasty

Step 2: then pour on the pasty mixture obtained in step 1 a water solution preferably added with a crosslinking agent (peroxide or platinum, alkaline solution, zinc oxide or magnesium), then intimately mixed a slip is obtained. The role of the crosslinking agent is to assist the branching of active-terminated fluid silicone homopolymers (1) on the ceramic micro-domains (2) CMD.

Step 3: It is then possible for example to impregnate a fibrous reinforcement, one then obtains a “ceramic composite with elastic matrix” then to place the assembly in a hermetic mold then to heat, for example to 60° C. during 40 minutes (or 6 minutes at 120° C.) to obtain a polycrystallization (2) of oxide ceramic, see FIG. 3 . (CMD). *In the case of solution 2, the proportion of homopolymers to be used, in mass of dry matter, can vary between 5% and 50% of the total matrix mass produced, depending on the type of flexibility sought.

The Si—O bonds are strong, it is greater than that of the C—O bonds; this gives the “elastic ceramic matrix composite” a: * great chemical inertia; * good resistance to UV (ultraviolet); * high degradation temperature: * Excellent ratings in fire resistance and smoke release.

A covalent bond is a strong chemical bond in which two atoms share two electrons (an electron each or two electrons from the same atom) of one of their outer layers to form a pair of electrons bonding the two atoms. It is one of the strongest forces that produce mutual attraction between atoms. Cyclic oligomers (Si—O)_(n), where n is between 2 and 5, has its oxygen atoms which are linked by double bond (covalent) to the silicon atoms of a ring where silicon atoms alternate with atoms of silicon and oxygen: in such a structure, oxygen is still divalent and silicon is still tetravalent.

In all Cases:

The preferred mineral ceramic matrix called “oxide ceramic” is chosen from the following materials:

1) A so-Called Class “A” of Alkali Ceramic Matrix:

Alcoholates [generic formula M(OR)_(n) where M is a metal or silicon and R is an organic alkyl C_(n)H_(2n+1)]; Tetrathoxysilane (TEOS); Alumina: micronized, pyrogenous Silica: micronized, precipitated, pyrogenized micronized magnesium oxide ie. (MgO) micronized zirconium oxide, namely. (ZrO₂); polysilanes [R1R2Si—R1R2Si]_(n), perhydropolysilazane [H₂Si—NH]_(n), polycarbosilanes [R1R2Si—CH₂]_(n) polysiloxanes [R1R2Si—O]_(n) polysilazanes [R1R2Si—NR3]_(n).

2) A so-Called “B” Class-Ceramic Mineral Matrix:

A mineral polymer, consisting of a poly(silico-oxo-aluminate) aluminosilicate, namely. (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅,Al₂O₂)_(n), which is designated resin, and a hardener, dissolved in an aqueous solution, constituted by at least one of hydroxyls of silicon (Si), aluminum hydroxyl (Al), magnesium hydroxyl (Mg), zirconium hydroxyl (Zr), calcium hydroxyl (Ca)), said hardener is obtained using one of the adjuvants mentioned below:

-   -   alkali adjuvant consisting of at least one of the following         bases: (KOH=potassium hydroxide, NaOH=sodium hydroxide).     -   acid adjuvant constituted by at least one of the following         acids: (HCl=hydrochloric acid, H₂SO₄=phosphoric acid,         HF=hydrofluoric acid).         -   a mineral polymer, consisting of a             poly(silico-oxo-aluminate) aluminosilicate, namely.             (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅,Al₂O₂)_(n)             supplemented with aluminum phosphate (AlPO₄), referred to as             resin, and a hardener, dissolved in a solution aqueous             solution consisting of at least one of the following             hydroxyls: (silicon hydroxyl (Si), aluminum hydroxyl (Al),             magnesium hydroxyl (Mg), zirconium hydroxyl (Zr), calcium             hydroxyl (Ca)) said hardener is obtained using one of the             adjuvants mentioned below:     -   alkali adjuvant consisting of at least one of the following         bases: (KOH=potassium hydroxide, NaOH=sodium hydroxide)     -   acid adjuvant constituted by at least one of the following         acids: (HCl=hydrochloric acid, H₂SO₄=phosphoric acid,         HF=hydrofluoric acid).         -   A mineral polymer consisting of a micronized alumina,             namely. (Al₂O₃) which is denoted by resin, and a hardener,             dissolved in an aqueous solution, constituted by at least             one of the following hydroxyls: (hydroxyl of silicon (Si),             hydroxyl of aluminum (Al), magnesium hydroxyl (Mg),             zirconium hydroxyl (Zr), calcium hydroxyl (Ca)), said             hardener is obtained by using one of the adjuvants mentioned             below:     -   an alkaline adjuvant consisting of at least one of the following         bases: (KOH=potassium hydroxide, NaOH=sodium hydroxide)     -   acid adjuvant constituted by at least one of the following         acids: (HCl, H₂SO₄, HF);         -   A complex mineral polymer consisting of a             poly(silico-oxo-aluminate) aluminosilicate, namely.             (—Si—O—Al—O—) n such as metakaolin (Si₂O₅,Al₂O₂)_(n) of a             micronized alumina namely. (Al₂O₃) which is denoted by             resin, and a hardener, dissolved in an aqueous solution,             constituted by at least one of the following hydroxyls:             (hydroxyl of silicon (Si), hydroxyl of aluminum (Al),             magnesium hydroxyl (Mg), zirconium hydroxyl (Zr), calcium             hydroxyl (Ca)), said hardener is obtained by using one of             the adjuvants mentioned below:     -   an alkaline adjuvant consisting of at least one of the following         bases: (KOH=potassium hydroxide, NaOH=sodium hydroxide)     -   acid adjuvant constituted by at least one of the following         acids: (HCl, H₂SO₄, HF);         -   A complex mineral polymer consisting of a             poly(silico-oxo-aluminate) aluminosilicate, namely             (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅,Al₂O₂)_(n)             micronized magnesium oxide ie. (MgO) which is denoted by             resin, and a hardener, dissolved in an aqueous solution,             constituted by at least one of the following hydroxyls:             (silicon hydroxyl (Si), aluminum hydroxyl (Al), magnesium             hydroxyl (Mg), zirconium hydroxyl (Zr), calcium hydroxyl             (Ca)), said hardener is obtained by using one of the             adjuvants mentioned below:     -   an alkaline adjuvant consisting of at least one of the following         bases: (KOH=potassium hydroxide, NaOH=sodium hydroxide)     -   acid adjuvant constituted by at least one of the following         acids: (HCl, H₂SO₄, HF); and more generally any ceramic matrix         known to those skilled in the art.     -   A network macro of reinforcing fibers in UD forms, fabrics,         braid, felt or matte; these functionalized fibers, or not         depending on their chemical composition, are chosen from         conventional reinforcement materials such as functionalized         boron fibers. *Functionalized silica. Functionalized Quartz         Basalt functionalized or not. *Functionalized glass.         *Unfunctionalized carbon. *Silicon carbide not functionalized.         *Functionalized ceramics (example alumina, or alumina mullite).         *Zirconium unfunctionalized. *Stainless steel functionalized.         *Inconel non functionalized Polysilazane functionalized.         *Aramid, non-functionalized. *HD polyethylene (Example: DYNEEMA)         not functionalized.

Preferably a micro reinforcement network as described in French Patent No. 14-02994 comprising functionalized dentritic nano-fractals (or not) characterized in that said dendritic nanofractals are either alkali-resistant or functionalized. This micro-network consists of dendritic nanofractals based on:

Metallic oxides, (titanium oxide TiO₂ zirconium oxide ZrO₂, etc.) non-functionalized metal oxides, (alumina Al₂O₃, etc.) functionalized or not Metalloid oxide such as silicon oxide=>silica: (silicon dioxide SiO₂), boron oxide=>boric anhydride: (borax anhydrous B₂O₃) functionalized or not metalloid oxide such as silicon carbide SiC no functionalized non-metals”, such as phosphorus oxide=>phosphoric anhydride (P₂O₅); carbon black which is colloidal carbon (graphite). Non functionalized.

According to one characteristic of the invention, the dendritic nanofractals consist of nanopatatoids of 10 to 50 nanometers in diameter aggregated with each other by covalent bonds to thereby form dendrites, circumscribed in a potatoid of 50 to 1000 nanometers in diameter, measured under an electronic microscope or laser granulometer; the values of the surface of said dendritic nanofractals are included in a range of values whose lower limit is about 10 square meters per gram and whose upper limit is about 750 square meters per gram, this value is called specific surface. The specific surface area of a powder is estimated from the amount of nitrogen adsorbed in relation to its pressure at the boiling point of liquid nitrogen and at normal atmospheric pressure. The information is interpreted according to the model of Brunauer, Emmett and Teller (BET method).

The expression “potatoïdes”, as used in the present description, means a form as defined for example in the dictionaries=A surface is called a patatoïde (or is called “patatoïdale”) when it is irregular and looks like an apple. ground (or “potato”). The term can be applied to a related volume in space but also to spherical or substantially spherical shapes. In topology, the Hausdorff dimension of a metric space (X, d) is a positive real number or zero, preferably random (non-homogeneous) lengths. In the aggregated structures of nanospheres implemented according to the invention, the Hausdorff dimension is between 1.5 and 2.5. These structures are called “dendritic nanofractals”. By “patatoid volume circumscribed to a dendritic nanofractal” is meant any three-dimensional volume, spherical or potatoid, including a cylinder. The statistical distance between two glass fibers in a matrix is of the order of 5,000 nanometers; it is therefore desirable, under these conditions, to have a large number of particles smaller than this size to avoid a “filtering” effect. The nanofractals of the composite matrix according to the invention respond well to this specification. It is referred to herein as “charges”, any type of functionalized or non-functionalized charges, that is to say any type of dendritic nanofractal described above. According to another characteristic of the invention, the dendritic nanofractals are in the form of at least one of the following structures: dendritic aggregates of nanopatatoids constituting dendritic nanofractals of chemical composition different from one dendritic nanofractal to the other; dendritic aggregates of nanopatatoids constituting dendritic nanofractals functionalized by functionalization agents of chemical composition different from a functionalized dendritic nanofractal to the other. “Accessible surface” means the entire surface of a dendritic nanofractal made of nanopatatoids which can be reached by a functionalizing agent on which it can be grafted, that is to say the surface unhindered by the presence of another nanopatatoid in the immediate vicinity which will cause a “steric hindrance” hindering the implantation of the functionalizing agent. It is possible to measure the average particle size using, for example, a laser diffraction particle analyzer. One can also use an electron microscope, for example scanning, and see the shape of the nanoparticles. To verify the presence of a mono-molecular layer, one can for example use a “tunnel electron microscope”. The key point of the process according to the invention consists in depositing the hydrolysis products, and then the surfactant, using the nano-aggregate as a nano reactor; the amount of water deposited will be calculated to exactly match the amount of water required for hydrolysis; because of surface tension phenomena, the water is evenly distributed in a nanometer-sized layer on the surface of the nano aggregate. Thus, when the surfactant “lands” on the water, it is hydrolysed on site and there is so little water that the surfactant cannot move to polycondense with a neighboring surfactant so it forms a very thin layer called mono molecular.

-   -   The “elastic microelements” (EME) (1) consist of linear elastic         molecular chains, terminated at their ends by functions capable         of chemically bonding to solid “micro ceramic domains” (MCD)         (2). This elastic network is preferably chosen from molecular         chains belonging to the family of fluid silicone homopolymers         (Polysiloxanes) with active terminations.

There are 5 main families of such homopolymers. These homopolymers are constituted by molecular chains:

-   -   I. OH terminated     -   II. H-terminated     -   III. Hybrid H-terminated on one side and OH on the other     -   IV. Alcohol-terminated (methanol or ethanol)     -   V. Vinyl-terminated

Polydimethylsiloxanes (PDMSs) are by far the largest volume of homopolymers produced. The molar mass is controlled by the addition of chain finishing monomers which may or may not be reactive. The purpose of the terminal reactive groups is to be able to cross-link the chains by condensation (amine, alkoxyl, hydroxyl, acetate, oxime, silanol, etc. groups) or radically (vinyl groups, etc.). The trimethylsiloxy-terminated polydimethylsiloxane is the most manufactured silicone. It is used as a fluid product, pasty or in the form of crosslinked elastomer. Due to the small intermolecular forces, the polymers always have boiling points and glass transition temperatures very low and, under normal conditions, they do not crystallize. The freedom of rotation around the siloxane bond gives the siloxane chains great flexibility, and compared to other polymers, small changes in physical properties with molar mass and temperature.

Typical Mechanical Properties

Hardness, shore A 10-90

Tensile stress 11 N/mm²

Elongation at break 100-1100%

Highest temperature +300° C.

Minimal temperature −120° C.

The “terminally active silicone homopolymers” described below are a non-exhaustive list of the EMEs that we claim:

I. OH-Terminated Molecular Chains

-   -   Siloxane chains, such as “silanol-terminated         poly(dimethylsiloxane)” are very flexible and rotation around         the Si—O axis is very easy, especially with small substituents.         Rotation is also possible around the Si—C axis for methyl         silicones. The freedom of rotation around the siloxane bond         gives the siloxane chains great flexibility, and compared to         other polymers, small changes in physical properties with molar         mass and temperature. FIG. 1 shows the chemical formula of         Poly(dimethylsiloxane), hydroxy terminated, or (Dimethiconol)         (case 31692-79-2) and FIG. 2 shows its spatial representation. *         The poly(dimethylsiloxane) terminated silanol (hydroxy         terminated) is the basic brick from which is obtained by         polymerization of silicone. The viscosity of this chain depends         on its length and thus on (n) number of repetitions of the base         unit (see FIG. 1 ). The viscosity in (mPas) at 25° C. varies         from 80 to 400,000. Preferably for the CCEM it is It is         preferable to use small monomers, therefore of low viscosity. *         Siloxane chains such as Silanol terminated polydimethylsiloxane         (case 70131-67-8) of molecular formula: HO[—Si(CH₃)₂O-]_(n)H     -   Siloxane chains such as vinylmethylsiloxane-dimethylsiloxane         copolymers, trimethyl (case 67923-19-7).

II. H-Terminated Molecular Chains

-   -   Chains such as Hydride terminated polydimethylsiloxane (Case         70900-21-9)     -   Chains such as Phenylsilsesquioxanes, hydrogen-terminated (Case         68952-30-7)

III. H-Terminated Hybrid Molecular Chains on One Side and OH on the Other

-   -   Chains such as Polytrifluoropropylmethylsiloxane, silanol         terminated

(Case 68607-77-2)

-   -   Chains such as 1,1,3,3-Tetramethyldisiloxane

(Cas 3277-26-7) of molecular formula C₄H₁₄OSi₂

-   -   Chains such as Hydride terminated polydimethylsiloxane (Case         70900-21-9)

IV. Molecular Chains with Alcohol Termination

-   -   Chains such as triethoxy (2,4,4-trimethylpentyl) silane

(Cas 35435-21-3) of molecular formula C₁₄H₃₂O₃Si

-   -   Chains such as Poly (methylhydrosiloxane)

(Cas 63148-57-2) of molecular formula C₇H₂₂O₂Si₃

-   -   Chains such as Poly (dimethylsiloxane-co-methylphenylsiloxane)

(Cas 63148-52-7) of molecular formula C₂₁H₂₄O₃Si₃X2

-   -   Chains such as Poly (dimethylsiloxane)

(Cas 63148-62-9) of molecular formula C₆H₁₈OSi₂

-   -   Chains such as Polydiethylsiloxane, triethylsiloxy terminated

(Cas 63148-61-8) of molecular formula C₆H₁₅OSi.(C₄H₁₀OSi)_(n).C₆H₁₅Si

-   -   Chains such as Poly [trifluoropropyl (methyl) siloxane]

(Cas 63148-56-1) of molecular formula (C₄H₇F₃OSi)_(n)

-   -   Chains such as Poly (methyl-3,3,3-trifluoropropylsiloxane)

(Case 115361-68-7)

-   -   Strings such as Methylhydrosiloxane, dimethylsiloxane copolymer,         trimethylsi (case 68037-59-2) of molecular formula C₃H₁₂OSi₂     -   Chains such as vinylmethylsiloxane-dimethylsiloxane copolymers,         trimethyl (case 67762-94-1) of molecular formula C₅H₁₄OSi₂

V. Molecular Chains with Vinyl Termination

-   -   Chains such as Vinyl terminated polydimethylsiloxane (case         68083-19-2)     -   Chains such as vinylmethylsiloxane, dimethylsiloxane copolymer,         vinyl terminated (case 68083-18-1)     -   Chains such as vinyl terminated poly-phenylmethylsiloxane (case         225927-21-9)     -   Chains such as vinyl terminated diphenylsiloxane,         dimethylsiloxane copolymer (case 68951-96-2)     -   Chains such as vinyl terminated trifluoropropylmethylsiloxane,         dimethylsiloxane copolymer (case 68951-98-4)

DESCRIPTION OF THE FIGURES

FIG. 1 is a chemical representation of an example of homopolymers of fluid silicone with active terminations (1) also called “elastic microelement” (EME). (In the example shown, it is an OH termination), where n is the number of iterations of the base module.

FIG. 2 is a spatial representation of an example of homopolymers of fluid silicone with active terminations (1) also called “elastic microelement” (EME).

FIG. 3 spatial representation of an example of solid “micro ceramic domains” (MCD) (2)

FIG. 4 spatial representation of an example of solid “micro ceramic domains” (MCD) (2) interconnected three-dimensionally by a dense network of “micro elastic elements” (EME) (1). This set constitutes an “elastic ceramic matrix” (ECM). It suffices to add to this matrix a network macro and preferentially a micro reinforcement network to result in an “elastic ceramic matrix composite” (ECMC)

FIG. 5 shows an example of polymerization=polycrystallization of a solid “ceramic micro-domain” (CMD) (2). Water (5) is used in which, for example, caustic soda (6) is dissolved in order to obtain a pH 11. The silica dispersed in this water is then converted into silicate (4). The liquid thus obtained is mixed with metakaolin (3). This gives a slip. During the polycrystallization, oxide ceramic crystals are obtained (2).

An alkaline solution is a solution of water in which we dissolved an alcaly such as: sodium hydroxide, or caustic soda (NaOH). *sodium carbonate (Na₂CO₃). *Potassium hydroxide, or caustic potash (KOH). *The K+ cation is less soluble in water than the Na+ cation. In addition, it is more difficult to complex, and can be more easily retained by compounds, such as clays. It is therefore more interesting in our applications.

Radical type vulcanization, of the fluid silicone homopolymer, can be carried out in a few minutes at temperatures above 110° C., using one or more organic peroxides (benzoyl peroxide and dicumyl peroxide for simplest cases) in low proportion (1 to 2%).

It is possible to cure with an organotannous catalyst (dibutyltin dilaurate), (nC₄H₉)₂Sn(OOCC₁₁H₂₃)₂), this reaction can be accelerated by the addition of a platinium salt. 

1. A production method of a ceramic composite with an elastic matrix, the method comprises the following steps: Step 1: an admixture comprising at least one of the following elements is dispersed in water an alkali an acid, to obtain “an adjuvant in aqueous solution”, Step 2: then, in the said adjuvant in aqueous solution, an additive is reacted to obtain a “mineral hardener” Step 3: Finally we prepare a “mineral resin powder” Step 4: said mineral hardener is poured and intimately mixed into said mineral resin powder to form a “ceramic mixture” the said process is characterized by the fact that the following steps that can be performed, either following or before some of the preceding steps, are added: Step 5: the preparation of a “fluid silicone homopolymer with active terminations” is carried out, Step 6: during this step, the dispersion of a homopolymer of fluid silicone with active terminations, is realized, either after step 3 or after step 4 to obtain said “elastic ceramic mixture”
 2. The method according to claim 1, further comprising: Step 7, consisting in impregnating said “elastic ceramic mixture” obtained at the end of step 6, with means of “fibrous reinforcements”, we then obtain a “ceramic composite with elastic matrix”
 3. The method according to claim 2, further comprising an additional step 8, of dispersing, in the mixture, a micro reinforcement network consisting of “dendritic nanofractals”.
 4. The method according to claim 3, wherein: “dendritic nanofractals” have so-called nanopatatoid forms (16) of 10 to 50 nanometers in diameter aggregated together by covalent bonds to thereby form dendrites (13, 15), circumscribed in a patatoid volume of 50 to 1000 nanometers in diameter, (the values of the surface of said dendritic nanofractals being included in a range of values whose lower limit is approximately 10 square meters per gram and whose limit higher, is about 750 square meters per gram (measured according to the BET)
 5. The method according to claim 3, wherein the dendritic nanofractals are formed based on a combination of at least one of the following products: Metal oxides, not functionalized Metal oxides, functionalized Metalloid oxide, functionalized Metalloid oxide, unfunctionalized Nonmetals, not functionalized.
 6. The method according to claim 1 wherein: —said alkali is constituted by a combination and at least one of the following bases: KOH=potassium hydroxide, NaOH=sodium hydroxide, CsOH=cesium hydroxide, LiOH=lithium hydroxide and the said acid being constituted by minus one of the following acids: HCl=hydrochloric acid, H2SO4=sulfuric acid, HF=hydrofluoric acid, H₃PO₄=phosphoric acid, to obtain an “adjuvant in aqueous solution” said additive is constituted by at least one of the following elements: an oxide (silicon, aluminum, magnesium, zirconium, calcium), a metal (aluminum, magnesium, zirconium, of calcium) a metalloid (of silicon), to obtain a “mineral hardener” said mineral resin powder consists of at least one of the following elements: a mineral polymer [consisting of a poly(sialate), (Si/Ai ratio=1)], a mineral polymer [consisting of a poly (sialate-siloxo), (Si/Ai ratio=2)], a polymer mineral [consisting of an aluminosilicate, poly(sialate-disiloxo), (Si/Ai ratio=3) namely (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅,Al₂O₂)_(n); A mineral polymer [consisting of an aluminosilicate, poly(sialate-disiloxo), namely (—Si—O—Al—O—)_(n) such as metakaolin Si₂O₅,Al₂O₂)_(n) supplemented with aluminum phosphate (AlPO₄); a complex mineral polymer [consisting of a poly(sialate-disiloxo) aluminosilicate, (Si/Ai ratio=3) namely (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅,Al₂O₂)_(n) and of a micronized alumina namely (Al₂O₃)]; A complex mineral polymer [consisting of a poly(sialate-disiloxo) aluminosilicate, (Si/Ai ratio=3) namely (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅,Al₂O₂)_(n) and d a micronized zirconium oxide, namely. (ZrO₂)]; a complex mineral polymer [consisting of a poly(sialate-disiloxo) aluminosilicate, (Si/Ai ratio=3) namely (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅,Al₂O₂)_(n) of micronized magnesium oxide namely (MgO)]; a complex mineral polymer [consisting of a poly(sialate-disiloxo) aluminosilicate, (Si/Al ratio=3) namely (—Si—O—Al—O—)_(n) such as metakaolin (Si₂O₅,Al₂O₂)_(n) of a micronized calcium oxide namely (CaO)] said active-terminated liquid silicone homopolymer of step 6 consists of at least one of the following terminations: OH-terminus, H-terminus, H-terminal hybrid on one side and OH on the other, termination alcohol (methanol), alcohol (ethanol) terminus, to obtain said “flexible ceramic mixture”.
 7. The method according to claim 3, wherein the “fibrous reinforcements” are chosen from at least one of the following functionalized fibers: *Bore fibers. *Silica functionalized. *Quartz functionalized. *Basalt preferentially functionalized. *Functionalized glass. *Carbon not functionalized. *Silicon carbide not functionalized. *Functionalized ceramics (eg alumina, alumina mullite). *Non-functionalized zirconium. *Stainless steel functionalized. * Inconel not functionalized. *Functionalized polysilazane. *Aramid, non-functionalized. *Polyethylene HD (Example DYNEEMA).
 8. The method according to claim 1, further comprising an additional step 8, of dispersing, in the mixture, a micro reinforcement network consisting of “dendritic nanofractals”.
 9. The method of claim 5, wherein the dendritic nanofractals are formed based on a combination comprising a functionalized metal oxide selected from a group consisting of titanium oxide and zirconium oxide.
 10. The method of claim 5, wherein the dendritic nanofractals are formed based on a combination comprising a functionalized metal oxide in the form of alumina.
 11. The method of claim 5, wherein the dendritic nanofractals are formed based on a combination comprising a functionalized metalloid oxide selected from a group consisting of silicon oxide, boron oxide, and boric anhydride.
 12. The method of claim 5, wherein the dendritic nanofractals are formed based on a combination comprising a unfunctionalized metalloid oxide in the form of silicon carbide.
 13. The method according to claim 3, wherein the dendritic nanofractals are formed based on a combination of at least one of the following products: Metal oxides, not functionalized Metal oxides, functionalized Metalloid oxide, functionalized Metalloid oxide, unfunctionalized Nonmetals, not functionalized.
 14. The method according to claim 3, wherein the dendritic nanofractals are formed based on a combination of at least one of the following products: a metal oxides, selected from the group consisting of TiO₂ titanium oxide and ZrO₂ zirconium oxide, not functionalized; alumina Al2O3, functionalized; a metalloid oxide, selected from the group consisting of silicon oxide, boron oxide, and boric anhydride, functionalized; SiC silicon carbide, unfunctionalized; and a nonmetal, selected from the group consisting of phosphorus oxide, phosphoric anhydride (P₂O₅), and carbon black, not functionalized.
 15. The method according to claim 4, wherein the dendritic nanofractals are formed based on a combination of at least one of the following products: a metal oxides, selected from the group consisting of TiO₂ titanium oxide and ZrO₂ zirconium oxide, not functionalized; alumina Al2O3, functionalized; a metalloid oxide, selected from the group consisting of silicon oxide, boron oxide, and boric anhydride, functionalized; SiC silicon carbide, unfunctionalized; and a nonmetal, selected from the group consisting of phosphorus oxide, phosphoric anhydride (P₂O₅), and carbon black, not functionalized. 